Azo dyestuffs



Patented June 20, 1939 UNITED STATES AZO DYESTUFFS Fritz Suckfiill, Leverkusen-Wiesdorf, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No DrawingJ- Application December 23, 1936,

Serial No. 117,340. 1936 3 Claims.

The present invention relates to new polyazo stuffs which may be represented by the following general formula:

In the said formula A means the radical of a diazotized amine or of a diazotized aminoazo compound, B means the radical of a diazotized amine coupled in para-position to the amino group, C means the radical of a diazotized aminoaroyl-amino-naphthol-monoor disulfonic acid and D means the radical of an aminoarylpyrazolone.

My new dyestuffs are obtainable by coupling a diazo compound or a diazoazo compound with an amine capable of coupling in para-position to the amino group, further diazotizing, again coupling with an aminoaroyl-aminonaphthol-monoor di'sulfonic acid, further diazotizing the polyazo dyestuff and finally coupling with an aminoaryl pyrazolone.

By this method new dyestuffs yielding in general brown shades further diazotizable in substance or on the fiber are obtained. The dyestuffs are also suited for after-treatment on the fiber with diazo compounds, as for example with diazotized paranitraniline.

The dyeings can be discharged well in a neutral medium; when D of the above general formula stands for the radical of an aminoarylpyrazolone- 3-carboxylic acid or a derivative thereof, dyestuffs are obtained which can be discharged well in a neutral and in an alkaline medium.

The invention is illustrated by the following examples; the parts being by weight.

OH: OCH:

s 053 OH; H

lilHz HO! 0H:

t OH: I and the amine is diazotized at 15 C. by adding, 69 parts'of sodium nitrite. After diazotization In Germany January 9,

is complete a solution of parts of cresidine of dyestuffs, more particularly it relates to azo dyethe formula:

O CH:

in 160 parts of hydrochloric acid (19 B.) and a small quantity of water are added and thereupon sodium acetate is added until the acid reaction to Congo red disappears. By heating to 40 C. coupling is finished, and the monoazodyestuff is isolated from the solution acid to Congo red.

The dyestuff paste is dissolved in water with the addition of sodium carbonate solution until the solution is neutral to litmus. After addition of 75 parts of sodium nitrite, 700 parts of hydrochloric acid (19 B.) are poured in at 15 C. while stirring. When the diazotization is complete the diazo compound is isolated by squeezing and addedto an aqueous solution of 360 parts of para-aminobenzoyl-2-amino 5 naphthol-l-sulionic acid and 280 parts of sodium carbonate. The disazo dyestuff obtained is isolated, suspended in Water and again diazotized at 18 C. after addition of 75 parts of sodium nitrite and 700 parts of hydrochloric acid (19 B.). After diazotization is complete a solution of 243 parts of l-metaaminophenyl-5-pyrazolone-3-carboxylic acid (sodium salt) and sodium acetate are added until the reaction is acid with acetic acid. After standing for several hours coupling is finished by addition of caustic soda lye until the reaction is alkaline. The dyestuff is squeezed off. It corresponds in its free state to the following formula:

It dyes when diazotized and developed on the fiber with ,8-naphthol or meta-phenylene diamine brown shades. The dyeings are easily dischargeable in a neutral and also in an alkaline medium. whenaft'er treated with diazotized para-nitraniline on the fiber, brown shades are likewise obtained.

On using as final coupling component parts of para-aminophenyl-3-methyl-5-pyrazolone, a dyestufi' is obtained which dyes cotton reddish brown after diazotizing on the fiber and developing with meta-phenylenediamine. This dyestuff is very easily dischargeable with a neutral discharge paste.

Example 2 By substituting 223 parts of a mixture of 1- naphthylamine-6- and 1-naphthylamine-7-su1- fonic acid for the cresidine of Example 1, there are obtained when diazotized on cotton and coupled with meta-phenylene diamine brown shades, which can be discharged very well in a neutral and also in an alkaline medium.

The dyestuif corresponds in its free state to the following formula:

parts of sodium nitrite are added. To the diazo compound thus formed 110 parts of metatoluidine dissolved in water and in 160 parts of hydrochloric acid (19 B.) are added. The cou- CH: NH.COC N=NCH-fi-COOH CH: N=N N= 60 S 0:11 I OH s 0&1 NH;

Example 3 in. The diazo compound is isolated after about 4 By using instead of the para-aminobenzoyl-Z- amino--naphthol-7-sulfonic acid of Example 1 an equivalent quantity of para-aminobenzoyl-2- anuno-8 naphthol-6-sulfonic acid, there are likewise obtained after developing brown shades of very good dischargeability.

The dyestuff corresponds in its free state to the following formula:

hours and. added to an aqueous solution of 110 parts of ortho-toluidine and l60parts of hydrochloric acid. Sodium acetate is added until the reaction is acid with acetic acid, whereby the coupling is completed. The aminodisazo dyestuif is isolated by squeezing from a solution acid to Congo red, dissolved with caustic soda lye and water until there is a neutral reaction, and by on; OCH; n: CHPQN=N N=N NH.COON=N(IEH(ITCOOH 00 N S 03H OH! I s 08H Example 4 the addition of 75 parts of sodium nitrite and 700 By using instead of the para-aminobenzoyl-2- amino-5-naphthol-7-sulfonic acid of Example 1, an equivalent quantity of pararaminobenzoyl-lamino-5-naphthol-7-sulfonic acid, lorowrt dyestuffs of similar properties are likewise obtaine'd; i

The dyestuff corresponds in its freestate to the following formula:

on, 0 CH:

s 08H' on, on V Example 5" a 303 parts of 2-naphthylamine-4.8-disulfonic acid are-dissolved in water and 335 parts of'hydrochloric acid (19 B.) and slowly at 10"C. '69

parts of hydrochloric acid (19 B.) diazotized at -18 C. After standing for several hours the diazo compound is added to an aqueous solution of 360 parts of para-aminobenzoyl-2-amino-5- naphthol-7-sulfonic acid and 300 parts of sodium carbonate. The trisazo dyestuff is isolated, suspended'in some water and again diazotized at 18 C. by adding 75 parts of sodium nitrite and CO N lsoin nncoOrwrwon-g-ooon 800 parts of hydrochloric acid (19 B.). Final coupling is effected with the sodium salt of 1- meta-aminophenyl-5 -"pyrazolone 3 carboxylic acid as described in Example 1;; When dyed' on cotton and developed-after diazotization with meta-phenylene diaminethereare obtained reddish brown shades of very good disoh'argeability both in a neutral and also in an alkaline medium.

The dyestufi corresponds in its free state to the following formula: A

manner to Example 1, finally diazotized and coupled with the sodium salt" of 'l-meta-aminophenyl-5-pyrazolone-3-carboxy1ic acid. After diazotizing and developing with meta-phenylene diamine there are obtained dark brown shades SOaH SOsH

Example 6 By Substituting 450 parts or para-aminobenzoyl-1-amino-8-naphthol-3.6 disulfonic acid SOaH 0011,

for the para-aminobenzoyl-Z-amino-5-naphtho1- 7-su1fonic acid of Example 5, there is obtained a dyestuff which yields when dyed on cotton, diazotized and developed with meta-phenylene diamine olive brown shades. The dyeings can be discharged to a pure white both in a neutral and also in an alkaline medium.

The dyestuft' corresponds in its free state to the following formula:

SOaH

Example 7 303 parts of 2-naphthy1amine-4.8-disulfonic acid are diazotized and coupled with 121 parts of para-xylidine, as described in Example 5, and after further diazotizing again coupled with 140 parts of cresidine, as indicated in-Example 5. After again diazotizing, the product is coupled with 360 parts of para-amino benzoyl-2-amino- 5-naphthol-7-sulfonic acid and in an analogous soul I =NON=NON=N Q (1118 (3151s I .L om s 03H which can be discharged to a pure white both in a neutral and also in an alkaline medium.

The d'yestufi corresponds in its free state to the following formula:

Example 8 223 parts of Z-naphthylamine-B-su1fonic acid are diazotized and coupled with 140 parts of cresidine, as indicated in Example 1. The aminoazo-d'yestuff is further diazotized with '75 parts of sodium nitrite and 700 parts of hydrochloric acid (19 B.) and coupled with 360 parts'of paraaminobenzoyl 2 amino 5 naphthol- 7-sulfonic acid in a soda alkaline medium. The final CON coupling is performed with l-meta-aminophenylpyrazolone-3-carboxylic acid, as indicated in Example 1.

After diazotizing and developing with metaphenylene-diamine there are obtained on cotton brown dyeings which can be discharged both in a neutral and also in an alkaline medium.

The dyestuff corresponds in its free state to the following formula:

SOaH

Iclaim: T Ki, 1. Azo dyestufi's having in, their freestate the I Hols following general formula:-

| CON NH: wherein A stands for aradical of the class consisting of benzene and naphthalene radicals, their homologues and alkoxy substituents which 2; Azo. dyestuffshav'ingintheir free state the following general formula:

do not contain further diazotizable amino groups, B stands for a member selected, from the group consisting of benzene and naphthalene radicals, their homologues and alkoxy substituents wherein the two azo groups are in para-position to each other, one of the radicals A and B containing at least one sulfonic acid radical, and 0 stands for a member selected from the group consisting'oi' radicals of aroyl-amino naphthol-monoand disulfonic acids, the azo group attached to the pyrazolone nucleus being also attached to the aroyl radical of said sulfonic acid, yielding in general brown shades.

yielding brown shades and; the dyeings being easily dischargeable in a neutral and also in an 40 alkaline medium. r

. r in FRITZ sUcKF'iiLL. 

